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Tobacco-specific nitrosamines (TSNAs) are one of the most extensively and continually studied classes of compounds found in tobacco and cigarette smoke.1−5 The TSNAs N-nitrosonornicotine (NNN) and 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) have been characterized by the US Food and Drug Administration (FDA) as harmful and potentially harmful constituents in tobacco products,6 and cigarette manufacturers report their levels in cigarette tobacco filler and cigarette smoke to the FDA. NNN and NNK are classified by IARC as carcinogenic to humans.7 TSNAs transfer from tobacco to smoke by evaporation driven by heat and the flow of gases down the cigarette rod. Other TSNA sources in smoke include pyrorelease, where room temperature-unextractable TSNAs are released by smoking, and pyrosynthesis, where TSNAs are formed by reactions during smoking. We propose the first model that quantifies these three sources of TSNA in smoke. In our model, evaporative transfer efficiency of a TSNA is equated to the evaporative transfer efficiency of nicotine. Smoke TSNA measured in excess of what is transferred by evaporation is termed “pyrogeneration,” which is the net sum of pyrorelease and pyrosynthesis minus pyrodegredation. This model requires no internal standard, is applicable to commercial cigarettes “as is,” and uses existing analytical methods. This model was applied to archived Philip Morris USA data. For commercial blended cigarettes, NNN pyrogeneration appears to be unimportant, but NNK pyrogeneration contributes roughly 30–70% of NNK in smoke with the greater contribution at lower tobacco NNK levels. This means there is an opportunity to significantly reduce smoke NNK by up to 70% if pyrogeneration can be decreased or eliminated, perhaps by finding a way to grow and cure tobacco with reduced matrix-bound NNK. For burley research cigarettes, pyrogeneration may account for 90% or more of both NNN and NNK in smoke.